Monoacylacetyl bodies containing azo or azoxy groups and process of making same



, waslun vention,

Patented Aug. 3, 1926.

Amanda zrrscnnn,

OF OFFENBACH-ON-THE-MAIN,

GERMANY, assrenon To '1. e.

FARBENINDUSTRIE AKTIENGESELLSCHAFT, 0F FRANKFOBT-QN-THE-MAIN, GER-MONOAOYTJACETYL BODIES CONTAINING MAKING SAME.

AZO OB AZOXY No Drawing. Application filed.Iune'7, 1923, Serial No.644,065, and in Germany Hay'S, 1923.

My invention relates to new monoacylace- 1 tylbodies of the generalformula:

Y-CO-GH,T-CONH R X-R',

wherein Y represents anyradicle of the hydrocarbon series containing atleast one and not more than six carbon atoms. R an aryl residue, R anaromatic residue, and X an azo or azoxy group.

Under the term an aromatic residue for R I include a carboorheterocyclic aromatic residue, substituted or not, as well the residueof an acyclic body containing a methylene group capable of combining. 4

The new bodies are obtained by heating acetoacetic acid ester or itshomologs "or analogs, such as benzoylacetic acid ester, withmonoaminobases corresponding to the formula, above mentioned, preferablyin a solvent or diluent.

As such aminoa'zoor -azoxycompound may be mentioned aminoazobenzene an-toluene, aminoazoxybenzene, the chlorinated and nitratedaminoazobenzenes, aminophenylazonaphthalene, benzeneazonaphthylamin,also aminoazocompounds, which can be obtained by combiningdiazotized'monoacyldiamins or nitroamins respectively of the aromaticseries with e. g. phenols or with bodies containing a methylene group,capable of combining, such as pyrazolones, or derivatives of ,8-ketonaldehyde, e. g. acetylacetone, derivatives of acetoaoetic acid andthe like, and by subsequently saponifying or reducing respectively theproducts obtalned.

The new bodies may products for the be used as primary sible theirfixation on the cotton fiber in alkaline solution and the developmentwith diazocompounds to valuable shades, fast to lollowing examplesillustrate the inthe parts being by weight.

Example 1.

The

' Asolutionofgfl parts of benzene-saw manufacture of dyestufis and theypossess in a surprising manner the character of a substantive bodymaking posproduct has the formula:

cmo 0.01m: o.nn-

Example Q.

39 parts of acetoacetic acid ester are run into a boiling solution of19.7 parts of 4- aminof-azobenzene in 250 parts of chlorobenzene whilestirring. The mixture is kept boiling, until the reaction is finished,and

the '-N-acetoacetyll-aminoazobenzene is iso- Crys lated in the abovedescribed manner. tallized from dilute alcohol it forms a yellowishorange-colored, finely crystalline powder, melting at 130131 (notcorrected). It is soluble in acetic acid ester, alco- GROUPS AND rnoonssor" feeble decomposition. It is, soluble in alcohol, insoluble in ether.This "ra I hol and ether, insoluble in carbon tetrachloride. Thisproduct has the formula:

Example 3.

reaction is worked upin ner. The -N-acetoacety1-4-aminobenzeneazo-lhenyl-3-methy1-5-pyrazolone is obtain as anorange-yellowlus r napry ttl the. described man-' line powder,decomposingat 208 rected). Grystallized from acetonitril it formsorange-yellow, fine lustrous needles,

having the same point of decomp is soluble in alcohol and acetonitril,insoluble in ether. This product has the formula:

cmcz r Instead of acetoacetic acid ester in each case its analogues suchas benzoylacetic acid ester may be used.

N Melting point -N-acetoacetyl-body from: Aspect. ga i O. not cor-Solubility.

i'ected. a 0i-tho-aminoazo-toluene. Orange-yellow, fine Dilute alcohol147 Soluble in alcohol and glacial acetic acid, insoluneedles. Die inether. Meta-aminoazo-toluene- Orange-colored, opales- Dilute alcohol133-134 Soluble in alcohol and glacial acetic acid, insolucant tinyscales. ble in ether. 4'-cliloi-o-4-aniino-azo-benzene Orange-yellow,fine, Dilute alcohol 188 Soluble in alcohol and glacial acetic acid,insoluclung needles. ble in ether. 3-nitro4-amino-azo-benzeneOrange-yellow, fine, Acetoacetic 138 under lee- Soluble in alcohol,glacial acetic acid and acetoclung needles. acid ester. ble tdecomaceticacid ester, insoluble in other.

I posi ion.

4-nitro-4-amino-azo-benzene Orange-red, lustrous I Acetoacetic scales.to

The following table gives the properties of some others of the compoundsobtainable according to the present process:

I 190491 under Soluble in alcohol and glacial acetic acid, insoluacid esr. zi ecomposible in ether. ion.

4-aminoazoxybenzene (iso- Feebly yellow little Dilute alcohol. 138underde- Soluble in alcohol and glacial acetic acid, insolumeric B,melting at 114' sheets. composition. ble in ether.

compare Chem. Centralblatt, 1921, III, age 780).4-amino-2-methy-benzene- Orange-yellow, conglo- Dilute alcohol. 153-154Soluble in alcohol and glacial acetic acid, less azo-Z-naphthalene. bateaggregates. soluble in ether. 4'-aminobenzene-azo-para- Clu ters oforange-yel- Aceto-nitril 165 Soluble in alcohol, glacial acetic acid andacecresol. i. w needles. tonitril, insoluble in ether. M

The N -acetoacetyl body from 4-aminoazoxybenzene has the formula:

CHLC 0.0H2-CO-NH Now what I claim and desire to secure by Letters Patentis the following:

1. As new articles monoacylacetylbodies of the general formula:

wherein R represents an aryl residue, R an aromatic residue, and an azoor azoxy group.

3. As new articles monoacetoacetylbodies of the general formula:

wherein R represents an aryl residue, R an aromatic residue, which arewhen dry ellow to red crystalline powders, soluble in dilute-causticsoda solution.

4. A process of making new monoacetoacetylbodies consisting in heatingacetoacetic acid ester with monoaminobases having the general formula:

wherein R represents aromatic residue.

5. A proeess of making new monoacetoacetylbodies which consists inheating acylacetic acid esters with monoaminobases having the generalformula:

wherein R represents an aryl residue, R an aromatic residue, and an azoor azoxy group, in a diluent.

6. A pfocess of making new monoacetoacetylbodies which consists inheating acetoacetic acid ester with monoaminobases having the generalformula:

wherein R represents an aryl residue, and

an aromatic residue, in a diluent. In testimony, that I claim theforegoing as my invention, I have signed this 23rd day of May 1923.

ARTHUR zirscnaa. a. .4.

an aryl residue, R an osition. It

y na

